Scribe coat on silver halide polyester film



Nov. 17, 1964 F. M. TRUSHEIM 3,

SCRIBE COAT UN SILVER HALIDE POLYESTER FILM Filed Dec. 28, 1959 TRANSPARE NT 22 POLYE THYLENE IO TERREPHTHALLATE SUBBING 11 MULTI COLOR DIAZOPRINT FIG. 2 V INVENTOR.

FRANK TRUSHEIM Y AT; gRIVEY-I-AGEIVT United States Patent 3,157,499SCREE CGAT 0N ILVER HALIDE P-SLYESTER FEM Frank M. Trnshehn, Gakhurst, N.11., assignor to Keufiel & Esser Co., Hoboken, Ni, a corporation of NewJersey Filed Dec. 28, 1959, Ser. No. 862,349 11 (Ilaims. (Qi. 96-27) Thepresent invention relates to drafting and more particularly to draftingon a scribe coat or peel coat on a base to obtain accurate lines andmore particularly relates to a scribe coat over a developable layer ofphotographic material adapted to receive selective colorings of selectedlines forming a master, for making photographic prints.

Heretofore, maps and the like have been made on a transparent basematerial coated with a scribable coat or peelable coat in which linesare formed by removing the scribe coat by a stylus, or cutting outlinesin a peel coat and removing the peel coat between the cut lines, therebyproviding lines for reproduction by photographic processes. The scribinghas been found advantageous because of the rapidity with which thedrafin can be done and because an operator can become sufiicientlyskilled after a short period of training to do satisfactory work.Although the previous processes have been satisfactory for Single color,it has not been practical to obtain multicolored lines or multi-coloredareas in a single master or stencil with the previously known methods,and therefore a separate scribed master or stencil was required for eachcolor to be reproduced on a finished map or the like.

There has always been a problem of obtaining correct registration of themasters or stencils when masters or stencils were used in providing thesuperimposed images in the final product such as a map of severaldifierent colors and consequently the prior methods of making maps orother graphic colored work have not been entirely satisfactory.

An object of the present invention is to provide a scribable coating onmaterial, a method of using the material, and a process of transferringthe information from the material to a final print in color by a directcontact process without requiring accurate registration of separatestencils.

A further object is to provide a scribable or peelable material on aphotographic base.

Another object is to provide a stencil material which is useful inmaking either a positive or negative from the same stock material, andis also useful in providing some portions positive and other portionsnegative on the same sheet.

A further object is to provide a method of producing selective coloredoutlines on a single sheet stencil or master.

Another object is to provide a master with selective portions thereofproviding filters for controlling the rays of light passing through theselected portions of the master.

Other and further objects will be apparent as the description proceedsand upon reference to the composition described and the drawing,wherein:

FIG. 1 is an isometric view showing the sequence of scribing a line tothe colored development of the selected lines and Q50 showing how largetransparent or opaque areas are produced in the master.

FIG. 2 is a developed diazo print made from the devel oped portion ofthe master shown in PEG. 1 showing how two colors the red and greenareas of the master print red and the black areas of the master printblack while the transparent portions of the stencil print white.

Briefly, the present invention includes a master sheet material having atransparent polyester base with progressively superposed layers ofphotosubbing, a silver halide emulsion and a pigmented organic scribecoating or a peelable coating in lieu of the scribe coating. With astylus an operator scribes a line through the scribe coating therebyuncovering the silver halide emulsion and said uncovered halide emulsionis developed with color formers or without color formers to obtainselected colored lines or black lines respectively. After one group oflines has been scribed such one group of lines is developed to producethe selected color, thereafter the same sheet of master material isscribed again for a second group of lines and such second group of linesis developed a different color and still other groups of lines arescribed and developed for as many different colors of lines as desired.If desired, the scribed line may be treated to provide a transparentline such as immersing the scribed line area in a bath of hypo fixingsolution to remove the silver halide. After the desired scribed lineshave been scribed and developed the pigmented organic scribe coat may beremoved from the background area with an organic solvent such as methylethyl ketone uncovering the photographic emulsion in the backgroundarea. If it is desired to have the background area of the stencil aparticular color the stencil is then developed the desired color. If thebackground is to be transparent the stencil is treated by fixing withoutdeveloping. If the background is to be black the background area isdeveloped and fixed in the conventional manner. The resulting master orstencil can then be placed in contact with a photosensitive sheetmaterial such as multi-color diazo paper and the diazo paper exposed,the various colored lines will filter out selected Wave lengths of lightthereby producing a multi-color diazo print.

Referring more particularly to FIG. 1 of the drawing, a transparent base16 of orientated polyethylene terephthalate is provided with aphotosubbing layer 11 on which a photosensitive layer of silver halideemulsion 12 is formed, and said silver halide emulsion is covered with apigmented organic scribe coating 13 of suitable materials such as thosedisclosed in application Serial No. 496,602, filed March 24, 1955, nowPatent 2,999,016.

A suitable scribe coating is described in Example IV in theaforementioned application as follows:

2 lbs. of alkyd resin 9 lbs. of titanium dioxide oz. cobalt naphthenatedrier 9 lbs. solvent (xylol, toluol and or ethyl acetate) if a coloredopaque scribe coating is desired, colored pigments such as chromeyellow, molybdate orange and carbon black may be added or suitablecolored dyes may be added.

A transparent coating would be obtained by leaving out all of thepigments and using only a dye opaque to actinic light. However, in thiscase the cutting properties would not be as good but could be improvedby additives without sacrificing much transparency.

Other resins may be added to these coatings. For example, urea andmelamine formaldehyde may be added up to about 10% of the resin content.Nitro cellulose may be added up to of the resin content if suitableplasticizers are also added.

Photosensitive coatings may be applied over these scribe coatings. Theseare useful so that an image can be reproduced on top of the scribingcoating and all or part of it cut into the scribing layer with asuitable tool.

The silver halide emulsion is sufficiently hard so that in scribingthrough the scribe coating 13 with a stylus 15 to uncover the emulsion12 therebelow as shown at scribe line 14 and the silver halide emulsionwill not be removed.

After scribing one group of lines to be made one color therebyuncovering the silver halide emulsion below the said one group of linesthe stencil sheet is treated a to produce the desired color of lines inthe uncovered silver halide emulsion in said one group by a knowndeveloping and fixing procedure. If it is desired to have a line or areabe transparent, the silver halide emulsion immediately beneath thescribed line areas to be transparent is treated to produce transparencyas by immersion of the scribed master sheet in a photographic hypofixing bath thereby removing the silver halide from the emulsion.

it is also possible to obtain selective coloring of the silver halideemulsion under any selected uncovered areas of such silver halideemulsion and this is accomplished by development of the uncoveredportion of the silver halide emulsion with photographic dye couplingdevelopers and color formers as hereinafter described.

Where a negative master is required, the scribe coating is scribed wherethe open window areas are required and treated with a hypo fixing baththereby removing the silver. Thereafter the pigmented organic scribecoating is removed by the organic solvent .by immersion in a bath of theorganic solvent and/or by wiping with a cloth soaked in the organicsolvent and uncovering the remainder of the silver halide, The emulsionis developed in the usual manner to obtain the desired color therebymaking an image in the selected color in the areas in which the scribecoating has just been removed while leaving the open window areas forthe transmission of light through the uncolored transparent areas wherethe silver halide has been removed.

It will be apparent that the method can be used in master materialhaving a peelable coat by removing selected areas of the peelable coatto be colored'a particular color.

Upon reference to FIG. 1, a scribe line 14 is made by means of ascribing tool 15 which removes the scribe coating 13 in the area of theline thereby uncovering the photographic emulsion 12 therebeneath. Ascribed line it? may be drawn to outline a closed area 17 and the scribecoating within the area may be removed by further. scribing or othermeans uncovering "the entire area 17 within the scribe line. Thescribe/coating within the line 16 may be removed by wiping with a clothsoakedin methyl ethyl ketone which will soften or dissolve the scribecoat to permit removal. The line 14 and the uncovered area 17 can bedeveloped by photographic processcs to obtain a colored line, a blackline, or an open window area. To demonstrate that all of such coloredlines, colored areas, transparent lines or open windows or transparentareas may be made in a single master or stencil, FIG. 1 has been drawnto illustrate the various areas and lines on a single master.

Where an area 1% is to be made green for example, the scribe or peelcoat is removed inthe desired area and the developing'is accomplished bydeveloping with a dye coupling developer in accordance with pages 16-150and 151 of Morgan and Lester, Photo Lab Index Quarterly Supplement,replacement pages 70 and 72, respectively, 4th quarter, 1956, and 2ndquarter, 1957, respectively; copyright, 1956, Morgan and Lester, 101Park Avenue, New York 17, New York. However applicant omits the initialdevelopment described in the Photo Lab index.

To illustrate the development of the area 19 to be made green, a stocksolution A of dye coupling'developer is made up according to thefollowingformula:

Water to make one liter.

This is the developing agent. It may be used *with all color formersbelow, but in the case of phitrophenylacetm nitrile'the magenta toneproduced tends toward the red. If a bluer magenta is desired, substitutefor the p-aminodietliylaniline hydrochloride an equal amount of2-amino-5-diethylaminotoluene hydrochloride.

The keeping qualities of this stock solution are poor. If it is to bekept for some time, the developing agent should be omitted, and addedjust before use.

For use: Add to each cc. of the above developer 10 cc. of one or amixture of the following color former solutions B. Mix together justbefore use and discard after the one use. The solution oxidizes rapidlyand must be used as soon as mixed. Exposure should be adjusted for atleast 3 minutes development at 68 F. (20 C.).

The following stock solutions B of color formers are provided:

Acetone to make 1 liter.

Green To obtain the green developed area 19, 19A after such area hasbeen uncovered by removal of the scribe coat 13 or peelable coat, themaster is developed in the mixture of solution A and solution Bz' 100cc. of solution Adye coupling developer 10 cc. of solution B (green)consisting of:

6 cc. of yellow color former of o-chloroacetoacetanilide in acetone 4cc. of cyan color former of 2,4-dichloro-1-naphthol in acetone (1) Theuncovered portion of'tne master was developed for 3 minutes in themixture of solution A (developer) and solution B (green color former)producing the green areas .19, 19A.

(1a) The master was washed to remove surplus developer.

(2) The uncovered portion of the master was bleached in a bleach bathmade up of the following:

Grams Potassium ferricyanide 30 Potassium bromide 15 Water to make 1liter.

The master was kept in the bleach for approximately 2 minutes.

(2a) The master was washed to remove the bleach.

(3) The uncovered portion of the master was fixed in an alkaline fixingbath or the following composition:

Sodium sulfite 40 grams. Hypo (sodium thiosulfate) 240 grams. Waterto'make 1 liter. Formaldehyde 100 cc. added to the'l liter 2 mixture.

(3a) The master was washed and dried.

Red

100 cc. of solution A (dye coupling developer) 7 10 cc. of solution B(red) consisting of:

8 cc. of yellow color former 2 cc. of magenta color former (1) Thestencil was developed for a period of 3 minutes in the mixture ofsolution A and solution 3 (red) producing a red image. I V

(1a) The master was washed to remove surplus devel-- oper.

ALL

ais'zaso (2) The uncovered portion of the master was then bleached in abath described above.

(2a) The master was washed to remove the bleach. (3) The uncoveredportion of the master was fixed in an alkaline fixing bath of thecomposition given above.

(30) The master was washed and dried.

Black A third area to be made black was then scribed in the areas 21,21A uncovering the silver halide emulsion and the master was developedin a conventional developer used for making a black image in a silverhalide emulsion and for this purpose any of the well known developersmay be used. The master was fixed in a fixing bath to fix the blackimage in the usual manner. Thereafter the master was washed and driedleaving the multi-color image areas in green, red and black.

Assuming that the background is to be transparent the remaining area ofthe scribe coating is then removed by any suitable means such as with acloth saturated with methylethyl-lietone or other suitable solvent. If apeelable coating is provided the remainder of the peelable coating isremoved by peeling. The remaining uncovered area is treated to provide atransparent background and for this purpose the master is immersed in analkaline fixing bath of the following composition:

Sodium sulfite 40 grams.

Hypo (sodium thiosulfate) 248 grams.

Water to make 1 liter.

Formaldehyde 100 cc. added to the 1 liter mixture.

The resulting stencil includes a green image, a rod image, and a blackimage with the background made transparent. It will be evident thatyellow, magenta or cyan areas may be obtained from the color formersshown, and many other colors may be provided.

It will thus be seen that a master can be made as a negative, apositive, a transparent positive or any combination thereof whereby asingle base sheet material may be used for many difierent purposes. Itwill also be evident that many different colors can be made in thestencil in accordance with the teachings in the Photo Lab Index. Thedifferent color areas may abut one another as shown in the red, greenand black areas 26A, 19A and 21A.

Where it is desired to have transparent lines in a black background,after the colored lines have been made, the transparent lines arescribed and the stencil immersed in the fixing bath thereby removing thesilver halide from the emulsion in the area of the transparent lines.After washing and drying the remaining scribe coat is removed and thestencil developed in conventional developer forming the black backgroundand is then fixed in a fixing bath.

The stencil made according to the above description may be used as amaster on a conventional diazo printer using a diazo material which willproduce multi-colors such as the diazo material of Leuch US. Patent2,659,672. Applicant has made a diazo print in which the black linesreproduce substantially black while the red and green lines reproducesubstantially red.

In the above process it will be evident that where two scribed linesintersect, the first development of the scribed lines is the color whichthe intersection takes and subsequent development does not affect thecolor of the intersection.

It will also be noted that the development for the conventional blackimage was scribed and developed subsequent to the various color dyeforming developments thereby avoiding any deleterious effects from thebleach used in the color forming development.

A suitable developer for the black image is hydroquinone which producesa high density image slowly and monomethyl-p-aminophenol sulfate whichproduces a lower density image fast and by suitable combinations 6thereof it is possible to get the desired rate of development and thedesired density.

The stencil made according to the present invention provides theequivalent of light filters in the colored areas thereby controlling thewave lengths of light which pass through the colored lines in thestencil thereby controlling the efiect of the light on the diazomaterial or other material with which the master is used in makingprints therefrom.

It will also be evident that the master may be used in a projector forviewing or for making photo copies by any suitable means.

The scribe coat may be marked in pencil or in any suitable way toindicate where the scribing is to be performed and for this purpose aphotosensitive material may be applied over the scribe coat as describedin the aforementioned application thereby making it possible for anoperator to accurately follow the outlines. It will also be apparentthat the outlines to be followed can be projected from a conventionalprojector such as is used in map making or the like.

It will be apparent that various changes may be made within the spiritof the invention as defined by the valid interpretation of the followingclaims.

What is claimed is:

l. The method of making a light transmitting master from a dimensionallystable light transmitting sheet material having a silver halide emulsionphotographic layer thereon and a selectively removable coat superimposedon the photographic layer, comprising removing said coat from a firstarea of appreciably less than the area of the sheet material uncoveringa first area of the photographic layer to permit developing fluids tocontact the first area of the photographic layer where the selectivelyremovable coat has been removed, and performing a developing operationon said first area of said photographic layer by a dye couplingdeveloper of sodium sulfate, sodium carbonate, potassium bromide, and acompound selected from the group consisting of p-aminodiethylanilinehydrochloride and 2-amino-5-diethylaminotoluene hydrochloride with atleast one color former from the group consisting of l-naphthol,2,4-dichloro-l-naphthol, o-phenyl phenol, 4-chloro-o-phenyl phenol,4,6-dibromo-o-cresol, 2,S-dichloroacetoacetanilide, acetoacetanilide,1-phenyl-3- methyl-S-pyrazolone, p-nitrophenylacetonitrile,o-chloroacetoacetanilide, and ethyl acetoacetate, t ereai'ter bleachingin a solution of potassium ferricyanide and potassium bromide, filingthe color in said first area, removing said coat from a second areauncovering a second area of said photographic layer and developing witha dye coupling developer and color former producing a difierent color inthe second area from the color in the first area, bleaching the secondarea, fixing the color image in said second area and repeating thesequence of operations for other areas to obtain a multi-colored masterof any desired number of areas.

2. The invention according to claim 1 in which one area is treated onlywith an alkaline fixing bath of sodium sulfite, hypo and formaldehyde.

3. The method of making a light transmitting master from a dimensionallystable light transmitting sheet material having a silver halide emulsionphotographic layer thereon and a selectively removable coat superimposedon the photographic layer, comprising removing said superimposed coatfrom a first area uncovering a first area of the photographic layer topermit developing fluids to contact the first area of the photographiclayer where the coat has been removed, and performing a developingoperation on said first area of said photographic layer by a dyecoupling developer of sodium sulfite, sodium carbonate, potassiumbromide, Z-amino-S-diethyl-aminotoluene, with o-chloroacetanilide2,4-dichloro-l-naphthol in acetone for 3 minutes then bleaching withpotassium ferricyanide and potassium bromide for 2 minutes, fixing thecolor in said first area with an alkaline fixing bath,

removing said coat from a second area uncovering a second area or" saidphotographic layer and fixing the second area of said photographic layerto obtain a transparent second area.

4. A method of producing colored lines in sheet material having a silverhalide emulsion layer thereon and a selectively removable scribe coatsuperimposed on the silver halide emulsion layer comprising scribinglines in a first area on the scribe coat to uncover a first area of thesilver halide emulsion layer therebeneath,

developing the first area of the silver halide emulison areas of thesheet in additional steps and developing such additional areas inadditional colors in respective additional steps thereby providing astencil having a plurality of difierently colored areas. 1

5. The invention according to claim 4 in which one area oi the silverhalide emulsion is made transparent by treating with a fixing bath. 6.A. method of producing distinctly different image reas in a sheetmaterial having a transparent base, a silver halide emulsion on the baseand a scribe coat on said silver halide emulsion and which scribe coatis removable by an organic solvent but which scribe coat is imperviousto materials used for developing silver halide on said silver halideemulsion comprising scribing the scribe coat with a closed line defininga first image area of the silver halide layer therebeneath, removing thescribe coat in said first image area within the closed line with anorganic solvent thereby uncovering the silver halide emulsion in saidfirst area, color developing the first image area to produce a firstcolor image in said first area of the photosensitive layer, fixing saidfirst image thereon, thereafter scribing a second area defining Y asecond image area and developing said second image area in adifferent'manner defining a second image distinctively difierent fromsaid first image, fixing said second image thereby making twodistinctiveimages in different areas.

7. The method of making a master comprising providing atransparent base,a silver halide emulsion layer on said base, a removable coat on saidsilver halide emulsion layer, said removable coat preventing materialsused for developing and fixing an image from contacting said silverhalide emulsion layer, and being accurately removable to accuratelyoutline image areas whereby the removable coat can be precisely removeduncovering the silver halide emulsion layer below said removed portionsof the coat, removing the coat in a first image area, developing thefirst image area in a first definite color and fixing the first definitecolor in said first image area with first materials to develop and .fixa first image, removing the coat in a second image area, developing saidsecond image area in a second color difierent from the first color ofthe first image area and fixing the second color in said second imagearea removable some with second materials to develop and fix a secondimage thereby providing a master with two distinct difierently coloredimage areas.

8. The method of making a master comprising providing atransparent-base, a silver halide emulsion on said base, a scribe coaton said silver halide emulsion, said scribe coat being impervious tomaterials used for developing and fixing an image from contacting saidsilver halide emulsion, saidscribe coat being accurately removable by ascribing action to accurately outline an image whereby the scribe coatcan be removed by a scribing action uncovering the silver halideemulsion which was beneath said removed portions of the scribe coat,accurately removing the scribe coat in a first image area uncovering thesilver halide emulsion in a first image area, developing the silverhalide emulsion in the first image area in a first definite color,fixing the first definite color in said first image area, thereafteraccurately re-' moving the scribe coat in a second image area uncoveringthe silver halide emulsion in the second image area, developing saidsilver halide emulsion in said second image area in a second colordifferent from the first color of said first image area, fixing thecolor in said second image area thereby providing a master with twodistinct differently colored image areas.

9. A master material comprising a transparent base, a silver halideemulsion layer on said base, a selectively removable coat superimposedon said silver halide emulsion layer, said removable coat preventingdeveloping.

materials used in developing and fixing an image-from contacting saidsilver halide emulsion layer, a photographic emulsion layer on saidremovable coat whereby a photographic image may be formed and developedon said photographic emulsion layer to serve as a guide for removing afirst selected area portion of said removable coat to uncover saidsilver halide emulsion layer in a desired first image area to bedeveloped into a predetermined color and thereafter may serve as a guidevfor removing a second selected area portion of said removable coat touncover a second image area of said silver halide emulsion layer andsuch second image area may be developed a second color different fromsaid first color.

10. The invention according to claim 9 in which the coat isdistinctively colored from the base and layers.

11. The invention according to claim 10 in which the removable coat is ascribe coat and is essentially an alkyd resin, and titanium dioxide.

References tilted by the Examiner UNITED STATES PATENTS 2,651,603 8/36Hruska 96-43 2,491,386 12/ 49 Miller et al 96-27 2,537,329 1/51 Campbell96-27 2,627,088 2/53 Alles et al. 96-87 2,718,476 9/55 Eichorn 96-27 XR2,810,661 10/57 Newman et al. 1l7138.8 XR 2,943,936 7/ Spechler 96-752,999,016 9/61 eeber et al 96-87 XR 3,023,099 2/62 Yaeger et al 96-91NORMAN G. TORCHIN, Primary Examiner.

HARGLD N. BURSTEIN, Examiner.

1. THE METHOD OF MAKING A LIGHT TRANSMITTING MASTER FROM A DIMENSIONALLYSTABLE LIGHT TRANSMITTING SHEET MATERIAL HAVING A SILVER HALIDE EMULSIONPHOTOGRAPHIC LAYER THEREON AND A SELECTIVELY REMOVABLE COAT SUPERIMPOSEDON THE PHOTOGRAPHIC LAYER, COMPRISING REMOVING SAID COAT FROM A FIRSTAREA OF APPRECIABLY LESS THAN THE AREA OF THE SHEET MATERIAL UNCOVERINGA FIRST AREA OF THE PHOTOGRAPHIC LAYER TO PERMIT DVELOPING FLUIDS TOCONTACT THE FIRST AREA OF THE PHOTGRAPHIC LAYER WHERE THE SELECTIVELYREMOVABLE COAT HAS BEEN REMOVED, AND PERFORMING A DEVELOPING OPERATIONON SAID FIRST AREA OF SAID PHOTOGRAPHIC-LAYER BY A DYE COUPLINGDEVELOPER OF SODIUM SULFATE, SODIUM CARBONATE, POTASSIUM BROMIDE, AND ACOMPOUND SELECTED FROM THE GROUP CONSISTING OF P-AMINODIETHYLANILINEHYDROCHORIDE AND 2-AMINO-5-DIETHYLAMINOTOLUENE HYDROCHLORIDE WITH ATLEAST ONE COLOR FORMER FROM THE GROUP CONSISTING OF 1-NAPHTHOL,2,4-DICHLORO-1-NAPHTHOL, O-PHENYL PHENOL, 4-CHLORO-O-PHENYL PHENOL,4,6-DIBROMO-O-CRESOL, 2,5-DICHLOROACETOACETANILIDE,ACETOACETANILIDE,1-PHENYL-3METHYL-5-PYRAZOLONE, P-NITROPHENYLACETONITRILE,O-CHLOROACETOACETANILIDE,AND ETHYL ACETOACETATE, THEREAFTER BLEACHING INA SOLUTION OF POTASSIUMFERRICYANIDE AND POTASSIUM BROMIDE, FIXING THECOLOR IN SAID FIRST AREA, REMOVING SAID COAT FROM A SECOND AREAUNCOVERING A SECOND AREA OF SAID PHOTOGRAPHIC LAYER AND DEVELOPING WITHA DYE COUPLING DEVELOPER AND COLOR FORMER PRODUCING A DIFFERENT COLOR INTHE SECOND AREA FROM THE COLOR IN THE FIRST AREA, BLEACHING THE SECONDAREA, FIXING THE COLOR IMAGE IN SAID SECOND AREA AND REPEATING THESEQUENCE OF OPERATIONS FOR OTHER AREAS TO OBTAIN A MULTI-COLORED MASTEROF ANY DESIRED NUMBER OF AREAS.